JPH1029836A - Method for producing quartz glass foam - Google Patents
Method for producing quartz glass foamInfo
- Publication number
- JPH1029836A JPH1029836A JP20282096A JP20282096A JPH1029836A JP H1029836 A JPH1029836 A JP H1029836A JP 20282096 A JP20282096 A JP 20282096A JP 20282096 A JP20282096 A JP 20282096A JP H1029836 A JPH1029836 A JP H1029836A
- Authority
- JP
- Japan
- Prior art keywords
- quartz glass
- glass foam
- producing
- foam
- foaming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/02—Pure silica glass, e.g. pure fused quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/80—Glass compositions containing bubbles or microbubbles, e.g. opaque quartz glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/50—After-treatment
- C03C2203/52—Heat-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
(57)【要約】
【課題】本発明は、均一な気泡径を有し、任意の発泡密
度の石英ガラス発泡体を製造する方法を提供すること。
【解決手段】アンモニア雰囲気中で加熱処理して得たア
ンモニア化非晶質シリカ母材を１４００〜１９００℃の
加熱雰囲気中で加熱発泡する石英ガラス発泡体の製造方
法において、前記加熱雰囲気の圧力を加熱開始から発泡
までを大気圧に維持し、発泡後は減圧状態とすることを
特徴とする石英ガラス発泡体の製造方法。(57) Abstract: The present invention provides a method for producing a quartz glass foam having a uniform cell diameter and an arbitrary foam density. In a method for producing a quartz glass foam in which an ammoniated amorphous silica base material obtained by heat treatment in an ammonia atmosphere is heated and foamed in a heating atmosphere at 1400 to 1900 ° C., the pressure of the heating atmosphere is reduced. A method for producing a quartz glass foam, comprising maintaining atmospheric pressure from the start of heating to foaming, and reducing the pressure after foaming.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、石英ガラス発泡体の製
造方法、さらに詳しくは均一な気泡直径を有し緻密な石
英ガラス発泡体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a quartz glass foam, and more particularly to a method for producing a dense quartz glass foam having a uniform cell diameter.
【０００２】[0002]
【従来技術】従来、石英ガラス発泡体は、軽量で、断熱
性が高い上に、低熱膨張性であるところから炉の保温断
熱構造材や軽量反射鏡の基体等に幅広く使用されてき
た。前記石英ガラス発泡体の製造方法としては、石英粉
もしくはガラス粉にカーボン粉や窒化珪素などの発泡剤
を添加混合し、それを発泡させる製造方法やアンモニア
化非晶質シリカ母材を１３５０〜１７００℃に加熱発泡
させる製造方法等（特開平１−３０８８４６号公報、特
開平５−３４５６３６号公報等）がある。前記発泡剤を
添加する製造方法では気泡径や見掛け密度の制御が困難
で、構造材料となるような緻密な石英ガラス発泡体の製
造が困難であった。そこで前記発泡時に１０ｋｇｆ／ｃ
ｍ2以下の圧力を掛け気泡径や見掛け密度を制御する方
法が特開平７−１６５４３４号公報で提案されたが、高
圧を必要とするところから、加熱炉の構築費用が増大し
製造コストを高いものにしていた。2. Description of the Related Art Conventionally, a quartz glass foam has been widely used as a heat insulating and heat-insulating structural material of a furnace, a base of a lightweight reflector, and the like because of its light weight, high heat insulating property and low thermal expansion property. As the method for producing the quartz glass foam, a production method in which a foaming agent such as carbon powder or silicon nitride is added to quartz powder or glass powder and mixed, and then foamed, or an ammoniated amorphous silica base material is used in a range of 1350 to 1700 There is a production method of heating and foaming at a temperature of, for example, JP-A-1-308846 and JP-A-5-345636. In the production method in which the foaming agent is added, it is difficult to control the cell diameter and apparent density, and it is difficult to produce a dense quartz glass foam as a structural material. Therefore, at the time of foaming, 10 kgf / c
A method of controlling the bubble diameter and the apparent density by applying a pressure of m 2 or less has been proposed in Japanese Patent Application Laid-Open No. 7-165434. However, since high pressure is required, the construction cost of the heating furnace is increased and the production cost is high. I was doing it.
【０００３】また、上記アンモニア化した非晶質シリカ
母材を発泡させる製造方法では発泡密度の制御を、原料
であるシリカ粉の粒度、発泡温度、発泡時間、アンモニ
ア化度等で行うが、発泡体のサイズが大きくなると見掛
け密度及び気泡径の制御が困難となり所望の発泡密度が
得られても均一な気泡直径を有する発泡体が製造できな
いといった欠点があった。そのためアンモニア化した非
晶質シリカ母材の発泡時に圧力をかける製造方法が特開
平５−１７１８０号公報で提案されたが、アンモニア化
した非晶質シリカ母材は、圧力をかけると発泡時に大き
く収縮し、石英ガラスの密度に近い発泡体となり軽量性
という利点が損なわれる欠点があった。[0003] In the above-mentioned production method for foaming an ammoniated amorphous silica base material, the foaming density is controlled by the particle size, foaming temperature, foaming time, degree of ammoniaation, etc. of the silica powder as a raw material. When the body size is large, it is difficult to control the apparent density and the cell diameter, and there is a drawback that a foam having a uniform cell diameter cannot be produced even if a desired cell density is obtained. For this reason, Japanese Patent Application Laid-Open No. 5-17180 proposes a production method in which pressure is applied during foaming of an ammoniated amorphous silica base material. There is a drawback that the foam shrinks and becomes a foam having a density close to that of quartz glass, and the advantage of lightness is impaired.
【０００４】[0004]
【発明が解決しようとする課題】こうした現状に鑑み、
本発明者等は、鋭意研究を続けた結果、アンモニア化さ
れた非晶質シリカ母材を加熱発泡するに当り加熱開始か
ら発泡時までを大気圧雰囲気とする一方、発泡後は徐々
に減圧状態とすることで発泡密度の制御が容易にでき、
均一な気泡径を有する石英ガラス発泡体が製造できるこ
とを見出し、本発明を完成したものである。すなわち、In view of the current situation,
The present inventors have conducted intensive studies, and found that when heating and foaming the ammoniated amorphous silica base material, the atmosphere from the start of heating to the time of foaming was set to an atmospheric pressure atmosphere, and after foaming, the pressure was gradually reduced. , The foam density can be easily controlled,
It has been found that a quartz glass foam having a uniform cell diameter can be produced, and the present invention has been completed. That is,
【０００５】本発明は、均一な気泡径を有する緻密な石
英ガラス発泡体の製造方法を提供することを目的とす
る。An object of the present invention is to provide a method for producing a dense quartz glass foam having a uniform cell diameter.
【０００６】また、本発明は、任意の気泡径と見掛け密
度を有する石英ガラス発泡体を容易に製造できる方法を
提供することを目的とする。Another object of the present invention is to provide a method for easily producing a quartz glass foam having an arbitrary cell diameter and an apparent density.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成する本発
明は、アンモニア雰囲気中で加熱処理して得たアンモニ
ア化非晶質シリカ母材を１４００〜１９００℃の加熱雰
囲気中で加熱発泡する石英ガラス発泡体の製造方法にお
いて、前記加熱雰囲気の圧力を加熱開始から発泡までを
大気圧に維持し、発泡後は減圧状態とすることを特徴と
する石英ガラス発泡体の製造方法に係る。SUMMARY OF THE INVENTION In order to achieve the above-mentioned object, the present invention provides a method for producing quartz by heating and foaming an ammoniated amorphous silica base material obtained by heat treatment in an ammonia atmosphere at a heating temperature of 1400 to 1900 ° C. In a method for producing a glass foam, the present invention relates to a method for producing a quartz glass foam, wherein the pressure of the heating atmosphere is maintained at an atmospheric pressure from the start of heating to foaming, and the pressure is reduced after foaming.
【０００８】上記製造方法で使用される非晶質シリカ母
材としては、精製し高純度のＳｉ（ＣＨ3）Ｃｌ3、Ｓｉ
Ｃｌ4等の珪素化合物を酸素、水素とともに加水分解用
バーナーに供給し、酸水素火炎で加水分解して得たすす
状シリカ微粒子をターゲット上に堆積させる方法、或は
アルコキシシランをアルコール溶媒中で酸及び／又は塩
基性触媒の存在下で加水分解し、それを加温条件下でゲ
ル化したのち、乾燥し、焼成ガラス化して得たガラス粉
末をポリビニルアルコール、カルボキシルメチルセルロ
ース、メチルセルロース等の結合剤を用いて母材に成形
する方法等で製造され、ＢＥＴ法で測定した比表面積が
４ｍ2／ｇ以上、ＯＨ基濃度が１００ｐｐｍ以上の非晶
質のシリカ母材が使用される。前記非晶質シリカ母材の
比表面積が４ｍ2／ｇ未満では十分な水酸基の置換除去
が進まず、耐熱性が低下するばかりでなく、アンモニア
の置換、吸着による導入量が減少し良好な気泡の形成が
できず、また、ＯＨ基濃度が１００ｐｐｍ未満ではアン
モニアの取り込み量が少なく同じように良好な気泡の形
成ができない。The amorphous silica base material used in the above-mentioned production method includes purified and high-purity Si (CH 3 ) Cl 3 , Si
A method in which a silicon compound such as Cl 4 is supplied to a burner for hydrolysis together with oxygen and hydrogen, and soot-like silica fine particles obtained by hydrolysis with an oxyhydrogen flame are deposited on a target, or alkoxysilane is dissolved in an alcohol solvent. A glass powder obtained by hydrolyzing in the presence of an acid and / or a basic catalyst, gelling it under a heating condition, and then drying and calcining the glass is used as a binder such as polyvinyl alcohol, carboxymethyl cellulose and methyl cellulose. An amorphous silica base material having a specific surface area of 4 m 2 / g or more measured by the BET method and an OH group concentration of 100 ppm or more is used. If the specific surface area of the amorphous silica base material is less than 4 m 2 / g, sufficient substitution and removal of hydroxyl groups will not proceed, and not only will the heat resistance be reduced, but the amount of introduction by ammonia substitution and adsorption will decrease, resulting in good air bubbles. If the OH group concentration is less than 100 ppm, the amount of ammonia taken in is small, and similarly good air bubbles cannot be formed.
【０００９】本発明の製造方法では、上記非晶質シリカ
母材をアンモニア雰囲気中で８００〜１３００℃に加熱
し、アンモニア化された非晶質シリカ母材を得、それを
加熱開始から取り込まれたアンモニアガスが離脱し発泡
するまでを、１ｋｇｆ／ｃｍ2の大気圧下で１４００〜
１９００℃の範囲の温度で加熱し、見掛け密度０．９ｇ
／ｃｍ3以上、好ましくは１〜１．４ｇ／ｃｍ3、気泡径
が３０〜１００μｍで構成された緻密な独立気泡群から
なる発泡体に成形する。次いで加熱温度を前記温度に維
持しながら雰囲気圧力を徐々に減圧状態に変え、形成さ
れている気泡径を増大させ石英ガラス発泡体とする。前
記減圧状態の真空度を任意に変えることで気泡径を任意
の大きさにできるので、例えば構造材のように機械的強
度の高い発泡体が必要な場合には、減圧度を低く押えて
発泡させ、反対に断熱材のように軽量性が重視される発
泡体が必要な場合には、減圧度を大きくして発泡させれ
ばよい。前記雰囲気圧力による発泡体の見掛け密度変化
を図１に示す。図１において横軸は雰囲気圧力（Ｔｏｒ
ｒ）、縦軸は見掛け密度（ｇ／ｃｍ3）を示すが、同図
から明らかなように真空度が高くなる程見掛け密度が小
さくなることがわかる。前記製造方法においてアンモニ
ア化温度が８００℃未満ではアンモニア化速度が遅く工
業的でなく、また温度が１３００℃を超えると、取り込
まれたアンモニアが発泡前に開放され低発泡となり好ま
しくない。また、減圧状態は徐々に行うのがよく、急激
な減圧では気泡径にバラツキが生じて好ましくない。In the production method of the present invention, the amorphous silica base material is heated to 800 to 1300 ° C. in an ammonia atmosphere to obtain an ammoniated amorphous silica base material, which is taken in from the start of heating. Until the ammonia gas is released and foams, the pressure is set at 1400 to 1 kgf / cm 2 at atmospheric pressure.
Heated at a temperature in the range of 1900 ° C, apparent density 0.9g
/ Cm 3 or more, preferably 1 to 1.4 g / cm 3 , and a foam formed of a dense closed cell group having a cell diameter of 30 to 100 μm. Then, while maintaining the heating temperature at the above temperature, the atmospheric pressure is gradually changed to a reduced pressure state, and the diameter of the formed bubbles is increased to obtain a quartz glass foam. Since the bubble diameter can be arbitrarily changed by arbitrarily changing the degree of vacuum in the reduced pressure state, when a foam having high mechanical strength is required, for example, a structural material, foaming is performed by lowering the reduced pressure degree. On the other hand, when a foam in which lightness is important such as a heat insulating material is required, the foam may be foamed by increasing the degree of pressure reduction. FIG. 1 shows a change in apparent density of the foam due to the atmospheric pressure. In FIG. 1, the horizontal axis represents the atmospheric pressure (Torr).
r), the vertical axis indicates the apparent density (g / cm 3 ). As is clear from the figure, the apparent density decreases as the degree of vacuum increases. In the above-mentioned production method, if the ammoniaation temperature is lower than 800 ° C., the ammoniaation rate is slow and not industrial, and if the temperature exceeds 1300 ° C., the taken-in ammonia is released before foaming, resulting in low foaming, which is not preferable. Further, it is preferable to gradually reduce the pressure, and if the pressure is reduced rapidly, the bubble diameter varies, which is not preferable.
【００１０】上述のとおり本発明では、高圧を特に必要
とすることなく均一な気泡径を有し、任意の見掛け密度
を有する発泡体を単に発泡時の雰囲気圧力を変えること
で製造でき、その製造コストを低く押さえることができ
工業的価値の高い石英ガラス発泡体の製造方法である。As described above, according to the present invention, it is possible to produce a foam having a uniform cell diameter without any special need for high pressure and an arbitrary apparent density simply by changing the atmospheric pressure during foaming. This is a method for producing a quartz glass foam having a low industrial cost and high industrial value.
【００１１】[0011]
【発明の実施の態様】次に具体例に基づいて本発明を詳
細に説明するが、本発明はそれにより限定されるもので
はない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to specific examples, but the present invention is not limited thereto.
【００１２】[0012]
実施例１ 四塩化珪素を酸水素火炎中で加水分解するＣＶＤ法によ
り、すす状シリカ微粒子をターゲット上に堆積させて非
晶質シリカ母材を製造した。前記非晶質シリカ母材をタ
ーゲットから抜き取り粉砕してフレーク状石英ガラス粉
にし比表面積をＢＥＴ法で測定したところ、４８ｍ2／
ｇであった。また、ＯＨ基濃度を赤外線吸光分光法で測
定したところ１１００ｐｐｍであった。前記石英ガラス
粉を石英ガラスの容器（内径４００ｍｍ×深さ３００ｍ
ｍ）の中に入れ、アンモニアガスを窒素ガス０．５Ｎｍ
3／ｈをキャリアガスとして、０．２Ｎｍ3／ｈ流しなが
ら電気炉にて８５０℃、５時間加熱保持した。アンモニ
ア化された石英ガラス粉を石英ガラス容器から取り出
し、内径３００ｍｍ、深さ４５０ｍｍのグラファイト製
容器中に移し、抵抗加熱式減圧炉に入れた。炉内雰囲気
を最初に１×１０-2Ｔｏｒｒまで減圧し石英ガラス粉に
含まれる気体を除去し、次いで不活性ガスである窒素ガ
スで置換し炉内雰囲気を大気圧とし、該圧力の状態で１
７８０℃で３０分間加熱保持し発泡させた。加熱温度を
前記温度に保持しつつ炉内雰囲気を大気圧から３８０Ｔ
ｏｒｒまで徐々に減圧し、さらに３０分間加熱保持し、
常温まで１０時間掛けて降温させた。得られた石英ガラ
ス発泡体は外径３００ｍｍ、高さ１４０ｍｍ、見掛け密
度０．７５ｇ／ｃｍ3、気泡平均径２１０μｍ、最大気
泡径３２０μｍであった。前記石英ガラス発泡体の断面
を観察したところ、空洞の発生はなく、独立気泡が均一
に分散していた。Example 1 An amorphous silica base material was manufactured by depositing soot-like silica fine particles on a target by a CVD method in which silicon tetrachloride was hydrolyzed in an oxyhydrogen flame. The place was specific surface area amorphous silica matrix to be withdrawn triturated from target flake quartz glass powder was measured by the BET method, 48m 2 /
g. The OH group concentration measured by infrared absorption spectroscopy was 1100 ppm. The quartz glass powder is placed in a quartz glass container (inner diameter 400 mm × depth 300 m)
m), and the ammonia gas is changed to 0.5 Nm of nitrogen gas.
3 / h was used as a carrier gas and heated at 850 ° C. for 5 hours in an electric furnace while flowing at 0.2 Nm 3 / h. The ammoniated quartz glass powder was taken out of the quartz glass container, transferred into a graphite container having an inner diameter of 300 mm and a depth of 450 mm, and placed in a resistance heating vacuum furnace. The atmosphere in the furnace was first reduced to 1 × 10 −2 Torr to remove the gas contained in the quartz glass powder, and then replaced with an inert gas such as nitrogen gas to bring the atmosphere in the furnace to atmospheric pressure. 1
The mixture was heated at 780 ° C. for 30 minutes to foam. While maintaining the heating temperature at the above temperature, the atmosphere in the furnace was changed from atmospheric pressure to 380T.
orr, gradually reduce the pressure, and heat and hold for 30 minutes,
The temperature was lowered to room temperature over 10 hours. The obtained quartz glass foam had an outer diameter of 300 mm, a height of 140 mm, an apparent density of 0.75 g / cm 3 , an average cell diameter of 210 μm, and a maximum cell diameter of 320 μm. Observation of the cross section of the quartz glass foam revealed that no voids were formed and closed cells were uniformly dispersed.
【００１３】実施例２ 実施例１と同様に、四塩化珪素を酸水素火炎中で加水分
解するＣＶＤ法により、得た非晶質シリカ粉をアンモニ
ア化したのち、内径６００ｍｍ、深さ３００ｍｍのグラ
ファイト製容器内に入れ、窒素ガスで置換して大気圧雰
囲気とし、１７８０℃で３０分加熱保持し発泡させた。
次いで前記１７８０℃の加熱温度に維持しつつ大気圧か
ら５０Ｔｏｒｒまで徐々に減圧し、さらに３０分間加熱
保持し、常温まで１０時間掛けて降温させた。得られた
石英ガラス発泡体は外径６００ｍｍ、高さ１００ｍｍ、
見掛け密度０．３５ｇ／ｃｍ3、気泡平均径７３０μ
ｍ、最大気泡径１２００μｍであった。石英ガラス発泡
体を切断しその断面を観察したが、空洞の発生がなく、
独立気泡が均一に分散していた。Example 2 In the same manner as in Example 1, the obtained amorphous silica powder was ammoniated by a CVD method in which silicon tetrachloride was hydrolyzed in an oxyhydrogen flame, and then graphite having an inner diameter of 600 mm and a depth of 300 mm was obtained. The mixture was placed in a container, and the atmosphere was replaced with nitrogen gas to obtain an atmospheric pressure atmosphere.
Next, the pressure was gradually reduced from atmospheric pressure to 50 Torr while maintaining the heating temperature of 1780 ° C., and the temperature was further maintained for 30 minutes, and the temperature was lowered to room temperature over 10 hours. The obtained quartz glass foam has an outer diameter of 600 mm, a height of 100 mm,
Apparent density 0.35g / cm 3 , average bubble diameter 730μ
m, and the maximum bubble diameter was 1200 μm. The quartz glass foam was cut and its cross section was observed.
The closed cells were uniformly dispersed.
【００１４】実施例３ 真空度を１９０Ｔｏｒｒとした以外、実施例１と同様に
して石英ガラス発泡体を製造した。得られた石英ガラス
発泡体の見掛け密度は０．４３ｇ／ｃｍ3、気泡平均径
は５６０μｍ、最大気泡径は８００μｍであった。石英
ガラス発泡体の断面を観察したが、空洞の発生がなく、
独立気泡が均一に分散していた。Example 3 A quartz glass foam was produced in the same manner as in Example 1 except that the degree of vacuum was changed to 190 Torr. The apparent density of the obtained quartz glass foam was 0.43 g / cm 3 , the average cell diameter was 560 μm, and the maximum cell diameter was 800 μm. The cross section of the quartz glass foam was observed.
The closed cells were uniformly dispersed.
【００１５】実施例４ 真空度を７６０Ｔｏｒｒとした以外、実施例１と同様に
して石英ガラス発泡体を製造した。得られた石英ガラス
発泡体の見掛け密度は１．２２ｇ／ｃｍ3、気泡平均径
は１００μｍ、最大気泡径は１５０μｍであった。石英
ガラス発泡体の断面を観察したが、空洞の発生がなく、
独立気泡が均一に分散していた。Example 4 A quartz glass foam was produced in the same manner as in Example 1 except that the degree of vacuum was changed to 760 Torr. The apparent density of the obtained quartz glass foam was 1.22 g / cm 3 , the average cell diameter was 100 μm, and the maximum cell diameter was 150 μm. The cross section of the quartz glass foam was observed.
The closed cells were uniformly dispersed.
【００１６】比較例１ 実施例１と同様に、四塩化珪素を酸水素火炎中で加水分
解するＣＶＤ法により得た非晶質シリカ粉をアンモニア
化したのち、内径６００ｍｍ、深さ４５０ｍｍのグラフ
ァイト製容器内に入れ、炉内圧力を１×１０-2Ｔｏｒｒ
まで減圧し、その真空度下で１７００℃に６０分加熱保
持し発泡させ、常温まで１０時間掛けて降温させた。得
られた石英ガラス発泡体は、外径３００ｍｍ、高さ１０
０ｍｍ、見掛け密度０．５３ｇ／ｃｍ3、気泡平均径６
２０μｍ、最大気泡径２００００μｍであった。前記石
英ガラス発泡体を切断しその断面を観察したところ、極
在的に大きな空洞があり、気泡径にも大きなバラツキが
あった。Comparative Example 1 In the same manner as in Example 1, amorphous silica powder obtained by a CVD method in which silicon tetrachloride is hydrolyzed in an oxyhydrogen flame was ammoniated and then made of graphite having an inner diameter of 600 mm and a depth of 450 mm. Put in a vessel and set the furnace pressure to 1 × 10 -2 Torr
The pressure was reduced to 1,700 ° C. for 60 minutes under the degree of vacuum, and foaming was performed. The temperature was lowered to room temperature over 10 hours. The obtained quartz glass foam has an outer diameter of 300 mm and a height of 10 mm.
0 mm, apparent density 0.53 g / cm 3 , average bubble diameter 6
20 μm and the maximum bubble diameter was 20,000 μm. When the quartz glass foam was cut and its cross section was observed, there was an extremely large cavity, and there was a large variation in the bubble diameter.
【００１７】比較例２ 実施例１と同様に、四塩化珪素を酸水素火炎中で加水分
解するＣＶＤ法により得た非晶質シリカ粉をアンモニア
化したのち、それを内径６００ｍｍ、深さ３００ｍｍの
グラファイト製容器内に入れ、炉内圧力を１×１０-2Ｔ
ｏｒｒまで減圧し、その真空下で１７００℃に１２０分
加熱保持し発泡させ、常温まで１０時間掛けて降温させ
た。得られた石英ガラス発泡体は、外径６００ｍｍ、高
さ１００ｍｍ、見掛け密度０．３５ｇ／ｃｍ3、気泡平
均径９００μｍ、最大気泡径４００００μｍであった。
前記石英ガラス発泡体の断面を観察したところ、内部に
多数の空洞があり、また空洞同志が連なっていた。Comparative Example 2 In the same manner as in Example 1, amorphous silica powder obtained by a CVD method in which silicon tetrachloride is hydrolyzed in an oxyhydrogen flame was ammoniated, and then the resultant was powdered with an inner diameter of 600 mm and a depth of 300 mm. Put in a graphite container and set the furnace pressure to 1 × 10 -2 T
The pressure was reduced to orr, and the mixture was heated and maintained at 1700 ° C. for 120 minutes under the vacuum to cause foaming, and then cooled to room temperature over 10 hours. The obtained quartz glass foam had an outer diameter of 600 mm, a height of 100 mm, an apparent density of 0.35 g / cm 3 , an average cell diameter of 900 μm, and a maximum cell diameter of 40,000 μm.
Observation of the cross section of the quartz glass foam revealed that there were many cavities inside and the cavities were continuous.
【００１８】[0018]
【発明の効果】本発明の製造方法では、均一な気泡径を
有する独立気泡が分散した任意の発泡密度の石英ガラス
発泡体が製造できる。前記製造方法は高圧用の加熱炉等
を必要とせず生産コストが安く、しかも使用原料を高純
度とすることで高純度の発泡体が製造でき、その工業的
価値は大きいものがある。According to the production method of the present invention, a quartz glass foam having an arbitrary foaming density in which closed cells having a uniform cell diameter are dispersed can be produced. The production method does not require a high-pressure heating furnace or the like, is low in production cost, and can produce a high-purity foam by using a high-purity raw material, and its industrial value is large.
【図１】雰囲気圧力と見掛け密度との関係を示すグラフ
である。FIG. 1 is a graph showing a relationship between an atmospheric pressure and an apparent density.
Claims (5)
ンモニア化非晶質シリカ母材を１４００〜１９００℃の
加熱雰囲気中で加熱発泡する石英ガラス発泡体の製造方
法において、前記加熱雰囲気の圧力を加熱開始から発泡
までを大気圧に維持し、発泡後は減圧状態とすることを
特徴とする石英ガラス発泡体の製造方法。1. A method for producing a quartz glass foam in which an ammoniated amorphous silica base material obtained by heat treatment in an ammonia atmosphere is foamed by heating in a heating atmosphere at 1400 to 1900 ° C. Is maintained at atmospheric pressure from the start of heating to foaming, and the pressure is reduced after foaming, thereby producing a quartz glass foam.
ｐｐｍ以下であることを特徴とする請求項１記載の石英
ガラス発泡体の製造方法。2. The method according to claim 1, wherein the metal impurities in the amorphous silica matrix are 100 or less.
The method for producing a quartz glass foam according to claim 1, wherein the content is not more than ppm.
以上、ＯＨ基濃度が１００ｐｐｍ以上であることを特徴
とする請求項１記載の石英ガラス発泡体の製造方法。3. The specific surface area of the amorphous silica matrix is 4 m 2 / g.
The method for producing a quartz glass foam according to claim 1, wherein the OH group concentration is 100 ppm or more.
ｏｒｒの範囲で選ばれることを特徴とする請求項１記載
の石英ガラス発泡体の製造方法。4. The reduced pressure state is from 1 Torr to 760 T in vacuum.
The method for producing a quartz glass foam according to claim 1, wherein the quartz glass foam is selected within the range of orr.
４０〜１３００μｍ、見掛け密度０．３ｇ／ｃｍ3〜
１．４ｇ／ｃｍ3の石英ガラス発泡体に発泡することを
特徴とする請求項１記載の石英ガラス発泡体の製造方
法。5. An ammoniated amorphous silica base material having a cell diameter of 40 to 1300 μm and an apparent density of 0.3 g / cm 3 to
2. The method for producing a quartz glass foam according to claim 1, wherein the foam is foamed into a 1.4 g / cm 3 quartz glass foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20282096A JP3883233B2 (en) | 1996-07-15 | 1996-07-15 | Method for producing quartz glass foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20282096A JP3883233B2 (en) | 1996-07-15 | 1996-07-15 | Method for producing quartz glass foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1029836A true JPH1029836A (en) | 1998-02-03 |
| JP3883233B2 JP3883233B2 (en) | 2007-02-21 |
Family
ID=16463745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20282096A Expired - Fee Related JP3883233B2 (en) | 1996-07-15 | 1996-07-15 | Method for producing quartz glass foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3883233B2 (en) |
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| EP1246325A3 (en) * | 2001-03-22 | 2004-08-25 | Matsushita Electric Industrial Co., Ltd. | Laser working dielectric substrate and method for working same and semiconductor package and method for manufacturing same |
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| WO2021172232A1 (en) * | 2020-02-28 | 2021-09-02 | Ａｇｃ株式会社 | Silica glass, high frequency device using silica glass, and silica glass production method |
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| JPWO2022215662A1 (en) * | 2021-04-07 | 2022-10-13 | ||
| CN117083252A (en) * | 2021-04-07 | 2023-11-17 | Ａｇｃ株式会社 | Silica glass components and methods of making the same |
| CN117303719A (en) * | 2023-08-17 | 2023-12-29 | 浙江大学 | A kind of high-purity opaque quartz glass ingot and preparation method thereof |
-
1996
- 1996-07-15 JP JP20282096A patent/JP3883233B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1164113A1 (en) * | 2000-06-12 | 2001-12-19 | Matsushita Electric Industrial Co., Ltd. | Method of laser machining glass substrate and method of fabricating high-frequency circuit |
| US6772514B2 (en) | 2000-06-12 | 2004-08-10 | Matsushita Electric Industrial Co., Ltd. | Method of machining glass substrate and method fabricating high-frequency circuit |
| EP1246325A3 (en) * | 2001-03-22 | 2004-08-25 | Matsushita Electric Industrial Co., Ltd. | Laser working dielectric substrate and method for working same and semiconductor package and method for manufacturing same |
| US7790078B2 (en) | 2005-02-14 | 2010-09-07 | Shin-Etsu Quartz Products Co., Ltd. | Process for producing silica glass product |
| CN115279705A (en) * | 2020-02-28 | 2022-11-01 | Ａｇｃ株式会社 | Silica glass, high-frequency device using silica glass, and method for producing silica glass |
| JPWO2021172232A1 (en) * | 2020-02-28 | 2021-09-02 | ||
| WO2021172232A1 (en) * | 2020-02-28 | 2021-09-02 | Ａｇｃ株式会社 | Silica glass, high frequency device using silica glass, and silica glass production method |
| KR20220147090A (en) * | 2020-02-28 | 2022-11-02 | 에이지씨 가부시키가이샤 | Silica glass, high frequency device using silica glass, and manufacturing method of silica glass |
| WO2022215663A1 (en) * | 2021-04-07 | 2022-10-13 | Ａｇｃ株式会社 | Silica glass member and method for producing same |
| JPWO2022215663A1 (en) * | 2021-04-07 | 2022-10-13 | ||
| JPWO2022215662A1 (en) * | 2021-04-07 | 2022-10-13 | ||
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| CN117303719A (en) * | 2023-08-17 | 2023-12-29 | 浙江大学 | A kind of high-purity opaque quartz glass ingot and preparation method thereof |
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